WO2007091391A1 - Procédé amélioré de production d'un dérivé de nitroguanidine - Google Patents

Procédé amélioré de production d'un dérivé de nitroguanidine Download PDF

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Publication number
WO2007091391A1
WO2007091391A1 PCT/JP2007/000066 JP2007000066W WO2007091391A1 WO 2007091391 A1 WO2007091391 A1 WO 2007091391A1 JP 2007000066 W JP2007000066 W JP 2007000066W WO 2007091391 A1 WO2007091391 A1 WO 2007091391A1
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WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
atom
salt
substituted
Prior art date
Application number
PCT/JP2007/000066
Other languages
English (en)
Japanese (ja)
Inventor
Hisato Kamekawa
Tomotaka Miyashita
Hiroyuki Katsuta
Toshio Kitashima
Original Assignee
Mitsui Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to ES07706314.7T priority Critical patent/ES2438979T3/es
Priority to CA2641877A priority patent/CA2641877C/fr
Priority to CN2007800049285A priority patent/CN101379035B/zh
Priority to EP07706314.7A priority patent/EP1985614B1/fr
Priority to AU2007213271A priority patent/AU2007213271A1/en
Priority to US12/278,497 priority patent/US7977496B2/en
Priority to JP2007557760A priority patent/JP4966210B2/ja
Publication of WO2007091391A1 publication Critical patent/WO2007091391A1/fr
Priority to IL193247A priority patent/IL193247A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical

Definitions

  • the present invention relates to an improved method for producing a nitroguanidine derivative having insecticidal activity.
  • a nitroguanidine derivative having insecticidal activity and a method for producing the same are disclosed in
  • JP-A-2-288860, JP-A-3-157308, JP-A-3-291267, and JP-A-7-179448 As represented by, for example, Japanese Patent Application Laid-Open No. 7-179448, the production method has many exchange reactions between isothiourea derivatives and amines, so that mercabtans having a bad odor are eliminated as a by-product. was there.
  • Japanese Patent Application Laid-Open No. 10-1 20666 discloses a compound represented by the general formula (B) by reacting an isourea compound represented by the general formula (A) or a salt thereof with an amine or a salt thereof.
  • Disclosed is a method for producing a guanidine derivative having insecticidal activity.
  • R represents an optionally substituted hydrocarbon group
  • R 2 represents hydrogen or an optionally substituted hydrocarbon group
  • Q represents an optionally substituted heterocyclic group
  • X represents Represents an electron withdrawing group
  • R 3 represents an optionally substituted amino group
  • R 2 , Q, and X represent the above-mentioned meanings.
  • Japanese Patent Application Laid-Open No. 2000-103776 discloses a method for producing a guanidine derivative having insecticidal activity by reacting an inexpensive nitroisourea derivative or a salt thereof with an amine or a salt thereof. It is disclosed.
  • Patent Document 1 Japanese Patent Laid-Open No. 2_288860
  • Patent Document 2 Japanese Patent Laid-Open No. 3_157308
  • Patent Document 3 Japanese Patent Laid-Open No. 3 291 267
  • Patent Document 4 Japanese Patent Application Laid-Open No. 7_179448
  • Patent Document 5 Japanese Patent Laid-Open No. 10-1 20666
  • Patent Document 6 Japanese Patent Laid-Open No. 2000_103776
  • An object of the present invention is to provide an industrially advantageous method for producing a guanidine derivative having insecticidal activity, which overcomes the above-mentioned drawbacks of the prior art. That is, An object of the present invention is to provide an improved production method capable of obtaining various guanidine derivatives having insecticidal activity with high selection and high yield while using an inexpensive nitroisourea intermediate.
  • R 2 represents an alkyl group having 1 to 4 carbon atoms or a benzyl group
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Q contains at least one nitrogen atom, oxygen atom or sulfur atom. And a 5- or 6-membered heterocyclic group which may be substituted with a halogen atom.
  • the heterocyclic group here is a pyridyl group, a pyridine mono-N-oxide group, a pyrimidinyl group, a pyridazyl group, a furyl group, a tetrahydrofuryl group, a chenyl group, a tetrahydrochenyl group, a tetrahydrobiranyl group, an oxazolyl group, an iso Xazolyl group, oxadiazolyl group, thiazolyl group, isothiazolyl group, thiadiazolyl group, pyrrole group, imidazolyl group, triazolyl group, virazolyl group, tetrazolyl group)
  • R 2 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Q represents a 5-membered or 6-membered heterocyclic group which contains at least one nitrogen atom, oxygen atom or sulfur atom and may be substituted with a halogen atom. And the meaning of the above.
  • the present invention provides a compound (1) or a salt thereof and an amine derivative (2) by reacting them in water in which an inorganic salt is dissolved at a saturation solubility of 50% or more.
  • the present invention relates to a method for producing an industrially advantageous compound (3) or a salt thereof capable of suppressing decomposition and further suppressing by-product formation by adding a base.
  • the nitroisourea derivative represented by the general formula (1) may contain a nitroisourea derivative having a double bond between the other nitrogen atom and carbon atom.
  • nitroguanidine derivative having an insecticidal action can be obtained with high selectivity and high yield, and can be produced industrially advantageously.
  • the method for producing a nitroguanidine derivative or a salt thereof of the present invention comprises a compound represented by the general formula (1)
  • R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Q contains at least one nitrogen atom, oxygen atom or sulfur atom.
  • R 2 represents an alkyl group having 1 to 4 carbon atoms
  • R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an alkyl having 1 to 4 carbon atoms
  • Q represents a 5-membered or 6-membered heterocyclic group which contains at least one nitrogen atom, oxygen atom or sulfur atom and may be substituted with a halogen atom. Represents the above-mentioned meaning.
  • the method of the present invention can suppress the decomposition of the raw material by reacting in water in which the inorganic salt is dissolved at a saturation solubility of 50% or more, and further by performing the reaction in the presence of a base.
  • R 4 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Q represents 5-membered or 6-membered heterocyclic group which contains at least one nitrogen atom, oxygen atom and sulfur atom and may be substituted with a halogen atom (the heterocyclic group here represents the above-mentioned meaning)
  • the production of by-products such as nitroisourea derivatives represented by [0032]
  • the nitroisourea derivative of the general formula (4) is subjected to the general formula (5) during the reaction.
  • R 4 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Q is 5-membered or 6-membered heterocyclic group which contains at least one nitrogen atom, oxygen atom and sulfur atom and may be substituted with a halogen atom (the heterocyclic group here represents the above-mentioned meaning) It is particularly important to suppress the formation of nitroguanidine derivatives represented by
  • the salt of compound (3), compound (1) and ammine derivative (2) may be any industrially acceptable salt, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, Inorganic acid salts such as sulfuric acid and perchloric acid or organic acids such as formic acid, acetic acid, tartaric acid, malic acid, citrate, oxalic acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid, p_toluenesulfonic acid Salt. Of these, hydrochloride and sulfate are preferable.
  • the amine derivative (2) is a known compound.
  • JP-A-5-286936, JP-A-7-1 79448, EP 44691 3A, JP-A-4_21 674, etc. It can be produced by the method described.
  • the amine derivative (2) or a salt thereof is the compound (1) or a salt thereof, It is used in an amount of 0.8 to 10 molar equivalents, preferably 0.9 to 1.5 molar equivalents. By reacting in such a numerical range, by-product formation is effectively suppressed, and the reaction of the amine derivative (2) or a salt thereof with the compound (1) or a salt thereof is selectively performed. Therefore, a guanidine derivative can be obtained in a high yield.
  • reaction selectivity By carrying out this reaction in the presence of a base, side reaction to the amine side can be suppressed and reaction selectivity can be improved.
  • Examples of such basic substances include alkali metal carbonates (eg, sodium carbonate, potassium carbonate, etc.), alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxides (eg, Examples are inorganic bases such as calcium hydroxide). In the present invention, one or more of these can be selected and used. These bases can be appropriately selected and used in the range of 0.05 to 5 times molar equivalent to the compound (1).
  • This reaction is carried out in a solid one-liquid two-layer system of water and compound (1) in which an inorganic salt dissolves at a saturation solubility of 500/0 or more, thereby suppressing decomposition of compound (1)
  • the yield can be improved.
  • the amount of these inorganic salts can be appropriately selected within the range of 50 to 100% saturated solubility, but 70 to 100% saturated solubility is preferable from the viewpoint of the above effects.
  • the saturated solubility of the inorganic salt is a value at the water temperature at the time of the reaction between the compound (1) and the compound (2).
  • the inorganic salt reduces the solubility of the compound (1) and at the same time functions as a cryogen. In this reaction, it is considered that the lower the initial reaction temperature, the more the decomposition of the compound (1) can be suppressed and the reaction selectivity can be improved.
  • the present inventors have conducted extensive research based on such findings and found that these effects can be obtained if the concentration of the inorganic salt is 50% or more of the saturation solubility.
  • lithium salts such as lithium chloride, lithium bromide, lithium iodide, lithium nitrate, and lithium sulfate, sodium chloride, sodium bromide, sodium bromide, and nitric acid.
  • Sodium salts such as sodium and sodium sulfate, potassium chloride, potassium bromide, potassium iodide, nitrate power Potassium salts such as lithium, potassium sulfate, potassium phosphate, etc., magnesium chloride, magnesium bromide, magnesium iodide, magnesium nitrate, magnesium sulfate, magnesium phosphate such as magnesium phosphate, calcium chloride, calcium bromide, calcium iodide
  • Calcium salts such as calcium nitrate, calcium sulfate, and calcium phosphate are used. In the present invention, one or more of these can be selected and used.
  • the amount of these inorganic salts is appropriately selected within the range of 50 to 100% saturation solubility.
  • the saturation solubility is defined as the relative value of the concentration of the inorganic salt that is actually dissolved when the saturated aqueous solution of the inorganic salt is assumed to have a saturation solubility of 1 000/0.
  • the saturated saline concentration at 20 ° C is about 26.4 wt%, so the saturated solubility of sodium chloride at 20 ° C is 50 to 100%. 13.2 to 26.4 wt% Means.
  • the reaction temperature is usually in the range of _30 to 100 ° C, preferably _20 to 50 ° C.
  • the reaction time is usually in the range of 10 minutes to 50 hours, preferably 1 hour to 25 hours.
  • R 2 are preferably each independently an alkyl group having 1 to 4 carbon atoms
  • R 3 is preferably a hydrogen atom
  • R 4 , R 5 and R 6 are each a hydrogen atom.
  • Q is preferably a 2_black mouth 5_thiazolyl group, a 2_black mouth 5_pyridinyl group, or a 3-tetrahydrofuranyl group because of its excellent insecticidal activity.
  • hydrochloric acid (6.7 g, 0.07 Mo I) was added to a pH of 4 or less.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Furan Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne un procédé amélioré de production d'un dérivé de nitroguanandine représenté par la formule générale (3) ci-dessous ou d'un sel de ce composé, qui possède une activité insecticide. Plus spécifiquement, l'invention concerne un procédé de production d'un dérivé de nitroguanidine représenté par la formule générale (3) ci dessous ou d'un sel de ce composé, un dérivé de nitro-iso-urée représenté par la formule générale (1) ci-dessous ou un sel de ce composé et un composé représenté par la formule générale (2) ci dessous ou un sel de celui-ci réagissant en présence d'une base dans une solution aqueuse, un sel inorganique étant dissout à au moins 50% de sa solubilité de saturation.
PCT/JP2007/000066 2006-02-10 2007-02-07 Procédé amélioré de production d'un dérivé de nitroguanidine WO2007091391A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
ES07706314.7T ES2438979T3 (es) 2006-02-10 2007-02-07 Procedimiento mejorado de producción de derivado de nitroguanidina
CA2641877A CA2641877C (fr) 2006-02-10 2007-02-07 Procede ameliore de production d'un derive de nitroguanidine
CN2007800049285A CN101379035B (zh) 2006-02-10 2007-02-07 硝基胍衍生物的经改良的制备方法
EP07706314.7A EP1985614B1 (fr) 2006-02-10 2007-02-07 Procédé amélioré de production d'un dérivé de nitroguanidine
AU2007213271A AU2007213271A1 (en) 2006-02-10 2007-02-07 Improved process for producing nitroguanidine derivatives
US12/278,497 US7977496B2 (en) 2006-02-10 2007-02-07 Process for producing nitroguanidine derivatives
JP2007557760A JP4966210B2 (ja) 2006-02-10 2007-02-07 ニトログアニジン誘導体の改良された製造方法
IL193247A IL193247A (en) 2006-02-10 2008-08-05 Process for making nitroguanidine history

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-033941 2006-02-10
JP2006033941 2006-02-10

Publications (1)

Publication Number Publication Date
WO2007091391A1 true WO2007091391A1 (fr) 2007-08-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/000066 WO2007091391A1 (fr) 2006-02-10 2007-02-07 Procédé amélioré de production d'un dérivé de nitroguanidine

Country Status (14)

Country Link
US (1) US7977496B2 (fr)
EP (1) EP1985614B1 (fr)
JP (1) JP4966210B2 (fr)
KR (1) KR101050018B1 (fr)
CN (1) CN101379035B (fr)
AU (1) AU2007213271A1 (fr)
CA (1) CA2641877C (fr)
ES (1) ES2438979T3 (fr)
IL (1) IL193247A (fr)
MX (1) MX295359B (fr)
RU (1) RU2008136366A (fr)
TW (1) TWI327138B (fr)
WO (1) WO2007091391A1 (fr)
ZA (1) ZA200806839B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104478762B (zh) * 2014-12-18 2017-01-11 湖南海利常德农药化工有限公司 N,o-二甲基-n-硝基异脲的制备方法
CN106316993B (zh) * 2016-07-28 2018-11-16 山东康乔生物科技有限公司 一种呋虫胺合成方法
CN106349196B (zh) * 2016-08-26 2019-01-04 江苏克胜作物科技有限公司 一种呋虫胺的合成方法
CN108358875A (zh) * 2018-03-02 2018-08-03 海利尔药业集团股份有限公司 一种呋虫胺的合成方法
CN109400552A (zh) * 2018-12-19 2019-03-01 江苏中谱检测有限公司 一种2-硝基-1，3-二[（四氢-3-呋喃）甲基]胍的合成制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000103776A (ja) * 1998-07-24 2000-04-11 Mitsui Chemicals Inc 新規ニトロイソウレア誘導体

Family Cites Families (10)

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Publication number Priority date Publication date Assignee Title
US242003A (en) * 1881-05-24 Plate-glass conveyer and setter
US2424003A (en) * 1944-12-08 1947-07-15 Jr Fred W Tanner Method for the production of riboflavin by candida flareri
JP2779403B2 (ja) 1988-11-29 1998-07-23 日本バイエルアグロケム株式会社 殺虫性ニトロ化合物
JP2546003B2 (ja) 1988-12-27 1996-10-23 武田薬品工業株式会社 グアニジン誘導体、その製造法及び殺虫剤
JPH0674249B2 (ja) 1990-04-05 1994-09-21 アグロカネショウ株式会社 置換ニトログアニジン類の製造法
US5434181A (en) 1993-10-26 1995-07-18 Mitsui Toatsu Chemicals, Inc. Furanyl insecticide
CN1072213C (zh) * 1995-06-23 2001-10-03 武田药品工业株式会社 胍衍生物的制备方法及其中间体
JP3413632B2 (ja) 1995-11-17 2003-06-03 住化武田農薬株式会社 グアニジン誘導体の製造方法
DE69900356T2 (de) * 1998-07-24 2002-07-11 Mitsui Chemicals Inc Nitro-Isoharnstoffderivate
JP2006103776A (ja) * 2004-10-08 2006-04-20 Toppan Printing Co Ltd 乾燥樹脂成形体が挿入された容器蓋

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000103776A (ja) * 1998-07-24 2000-04-11 Mitsui Chemicals Inc 新規ニトロイソウレア誘導体

Also Published As

Publication number Publication date
KR20080091497A (ko) 2008-10-13
ES2438979T3 (es) 2014-01-21
IL193247A0 (en) 2009-02-11
IL193247A (en) 2014-03-31
AU2007213271A1 (en) 2007-08-16
EP1985614A4 (fr) 2010-10-20
MX295359B (en) 2012-01-27
CA2641877C (fr) 2011-03-29
EP1985614B1 (fr) 2013-09-25
MX2008010143A (es) 2008-08-19
TWI327138B (en) 2010-07-11
US7977496B2 (en) 2011-07-12
CN101379035B (zh) 2011-01-12
KR101050018B1 (ko) 2011-07-19
EP1985614A1 (fr) 2008-10-29
US20090176990A1 (en) 2009-07-09
CA2641877A1 (fr) 2007-08-16
RU2008136366A (ru) 2010-03-20
JPWO2007091391A1 (ja) 2009-07-02
ZA200806839B (en) 2009-11-25
JP4966210B2 (ja) 2012-07-04
CN101379035A (zh) 2009-03-04
TW200745038A (en) 2007-12-16

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